DE69930667T2 - THERMOPLASTIC FIBERS AND TEXTILE SURFACE IMAGES - Google Patents

Description

The The present invention relates to thermoplastic fibers and fabrics.

It is known fibers, yarns and fabrics of polystyrene, vinyl polymers, various types of nylon, polyesters, polyolefins or fluorocarbons manufacture. See, for example, U.S. Patents 4,181,762; 4,945,150; 4,909,975 and 5,071,917.

It is still desirable, To provide fibers made from polymers containing not as starting materials for the production of fibers, yarns and fabrics were used. These fibers have extraordinary Properties relating to bonding, hydrophilicity and chemical resistance, which is a special feature of epoxy based polymers.

In A first embodiment is in the present Invention to a fiber of at least one thermoplastic hydroxy-functionalized Polyether and, optionally, a thermoplastic polymer, the is not a hydroxy-functionalized polyether.

In a second embodiment is in the present Invention to a bicomponent fiber with (1) a first component from a thermoplastic hydroxy-functionalized polyether or a mixture of a hydroxy-functionalized polyether and (2) a second component of a thermoplastic polymer, the is not a hydroxy-functionalized polyether.

In a third embodiment is in the present Invention by a method for producing a nonwoven fabric by Forming a web of at least one fiber component and heating the web Fleece, so that the fiber components of the nonwoven stick, thereby characterized in that at least one fiber component of a thermoplastic hydroxy-functionalized polyether.

The Fiber of the present invention may be a monocomponent fiber or be a bicomponent fiber.

The Monocomponent fiber consists of at least one thermoplastic hydroxy-functionalized polyether and, optionally, a thermoplastic Polymer that is not a hydroxy-functionalized polyether.

in the Generally, the thermoplastic hydroxy-functionalized Polyethers prepared by the reaction of a dinucleophilic monomer with a diglycidyl ether, a diglycidyl ester or epihalohydrin.

• (1) Polyetheraminen mit Grundeinheiten, die repräsentiert werden durch die Formel:
  
• (2) hydroxyfunktionalisierten Polyethern mit Grundeinheiten, die repräsentiert werden durch die Formel:
  
  oder
• (3) hydroxyfunktionalisierten Poly(ethersulfonamiden) mit Grundeinheiten, die repräsentiert werden durch die Formel:
  
  oder
  
  wobei R⁵ Wasserstoff oder Alkyl ist; R⁷ und R⁹ unabhängig voneinander Alkyl, substituiertes Alkyl, Aryl, substituiertes Aryl sind; R⁸ eine zweiwertige organische Komponente ist, die hauptsächlich Kohlenwasserstoff ist; A eine Aminkomponente oder eine Kombination von verschiedenen Aminkomponenten ist; B eine zweiwertige organische Komponente ist, die hauptsächlich Kohlenwasserstoff ist; und m eine ganze Zahl von 5 bis 1000 ist.

Preferably, the thermoplastic hydroxy-functionalized polyether is selected from:

• (1) Polyetheramines having repeating units represented by the formula:
  
• (2) hydroxy-functionalized polyethers having repeating units represented by the formula:
  
  or
• (3) hydroxy-functionalized poly (ether sulfonamides) having repeating units represented by the formula:
  
  or
  
  wherein R ^{5 is} hydrogen or alkyl; R ⁷ and R ^{9 are} independently alkyl, substituted alkyl, aryl, substituted aryl; R ^{8 is} a divalent organic component which is mainly hydrocarbon; A is an amine moiety or a combination of different amine moieties; B is a divalent organic component which is mainly hydrocarbon; and m is an integer of 5 to 1000.

In the preferred embodiment of the present invention A is 2-hydroxyethylimino, 2-hydroxypropylimino, piperazenyl, N, N'-bis (2-hydroxyethyl) -1,2-ethylenediimino; and B and R 'are independently of each other 1,3-phenylene, 1,4-phenylene, sulfonyldiphenylene, oxydiphenylene, thiodiphenylene or isopropylidenediphenylene; R ⁵ is hydrogen; R ⁷ and R ⁹ are independently methyl, ethyl, propyl, butyl, 2-hydroxyethyl or phenyl; and B and R ⁸ are independently 1,3-phenylene, 1,4-phenylene, sulfonyldiphenylene, oxydiphenylene, thiodiphenylene or isopropylidenediphenylene.

The represented by formula I. Polyetheramines, also referred to as poly (hydroxyamino ethers), are prepared by adding one or more diglycidyl ethers of a divalent Phenols with an amine with two amine hydrogens under conditions be contacted so that the amine components are sufficient react with epoxide components to form a polymer backbone with amine linkages, Ether bonds and hydroxyl side groups to form. These polyether amines are described in U.S. Patent 5,275,853. The polyetheramines can also be prepared by a diglycidyl ether or an epihalohydrin is contacted with a difunctional amine.

The represented by formula II hydroxy-functionalized polyethers are prepared by, for example a digylcidyl ether or a combination of diglycidyl ethers with a dihydric phenol or a combination of divalent ones Phenols according to the method described in US Patent 5,164,472 is brought into contact. Alternatively, the poly (hydroxy ether), if you have a dihydric phenol or a combination of divalent ones Phenols after that of Reinking, Barnabeo and Hale in the Journal of Applied Polymer Science, Vol. 7, p. 2135 (1963) React process with an epihalohydrin.

The represented by formula IIIa and IIIb hydroxy-functionalized poly (ether sulfonamides) are prepared, by, for example, an N, N'-dialkyl or N, N'-diaryldisulfonamide is polymerized with a diglycidyl ether, as in the US Patent 5,149,768.

The hydroxy-functionalized polyethers commercially available from Phenoxy Associates, Inc. are also suitable for use in the present invention. These hydroxy-functionalized polyethers are the condensation reaction products of a dihydric polynuclear phenol, such as bisphenol A, and an epihalohydrin, and have the repeating units represented by Formula II, in which B is an isopropylidenediphenylene moiety. These hydroxy-phenoxyether polymers and the process for their preparation are described in U.S. Patent 3,305,528. Other hydroxy-functional polyethers suitable for use in the present invention are poly (alkylene oxides) which are normally prepared by the polymerization of ethylene oxide, propylene oxide or butylene oxide. Specific examples include poly (ethylene oxide), poly (propylene oxide), poly (butylene oxide), or copolymers containing various amounts of other poly (alkylene oxides). Under certain circumstances, these polymers are also particularly suitable for mixing with polymers of any of formulas I to III. Among the advantages of the mixtures of poly (alkylene oxides) and polymers of formulas I to III is that the glass transition temperature of the mixtures can be manipulated or the hydrophilicity can be modified.

To the polymers which are not hydroxy-functionalized polyethers, in the practice of the present invention for Manufacture of the fibers may include polyolefins, polyesters, Polyamides, polysaccharides, modified polysaccharides or naturally occurring ones Fibers or particulate fillers; thermoplastic polyurethanes, thermoplastic elastomers and glycol-modified copolyesters (PETG). Other polyester or polyamide type polymers may be used in practical use of the present invention also used to make the fiber become. These polymers include Poly (hexamethylene adipamide), polycaprolactone, poly (hexamethylene sebacamide), Poly (ethylene 2,6-naphthalate) and polyethylene 1,5-naphthalate), poly (tetramethylene 1,2-dioxybenzoate) and copolymers of ethylene terephthalate and ethylene isophthalate.

The Polyesters and processes for their preparation are known in the art well known, and for the purposes of this invention will be referred to. As an illustration and not for limitation in particular, pages 1-62 of volume 12 of the Encyclopedia of Polymer Science and Engineering, 1988 version, John Wiley & Sons, directed.

The Polymers which are not hydroxy-functionalized polyethers can be described in US Pat Amounts of less than 50% by weight and preferably less than 30 Wt .-%, based on the weight of the fiber, with the hydroxy-functionalized Polyether can be mixed. These other polymers can the hydroxy-functionalized polyethers are added to the production cost to reduce the physical properties, barrier or Permeability characteristics or the adhesion characteristics to modify. For the bicomponent fibers, the separate, no functional hydroxyl-containing component in quantities up to 99 percent, preferably less than 95 percent on the weight of the fiber, to be used.

To polyamides used in the practical application of the present Invention can be used to produce the fibers include the various types of nylon, such as nylon 6, nylon 6,6 and Nylon 12th

Under The term "polyolefin" is a simple one Olefin monomers such as ethylene, propylene, butylene or To understand isoprene-derived polymer or copolymer, and a or more monomers copolymerizable therewith. Such polymers (including raw materials, their proportions, polymerization temperatures, catalysts and others Conditions) are well known in the art, and for the purposes of this Invention is referred to. To other comonomers, the can be polymerized with ethylene include olefin monomers with 3 to 12 carbon atoms, ethylenically unsaturated carboxylic acids (both mono- as well as difunctional) and derivatives of such acids, such as for example, esters (for example, alkyl acrylates) and anhydrides; monovinylidene aromatics and monovinylidene aromatics substituted with a component other than halogen, such as styrene and methylstyrene; and carbon monoxide. To exemplary monomers that can be polymerized with ethylene include 1-octene, Acrylic acid, Methacrylic acid, vinyl acetate and maleic anhydride.

Polyolefins that can be used in the practice of the present invention to make the fibers include polypropylene, polyethylene and copolymers and blends thereof, and ethylene-propylene-diene terpolymers. Preferred polyolefins are polypropylene, such as Pro-fax ^™ PF635 (trademark of Montell North American Inc.) and INSPIRE ^™ (trademark of The Dow Chemical Company), linear high density polyethylene (HDPE), heterogeneously branched linear low density polyethylene (LLDPE ), such as DOWLEX ^™ polyethylene resin (trademark of The Dow Chemical Company), ultra-low density heterogeneously branched linear polyethylene (ULDPE) such as ATTANE ^™ ULDPE (trademark of The Dow Chemical Company); homogeneously branched linear ethylene / α-olefin copolymers such as Tafmer ^™ (trademark of Mitsui Petrochemicals Company Limited) and Exact ™ (trademark of Exxon Chemical Company); homogeneously branched, substantially linear ethylene / α-olefin polymers such as AFFINITY ^™ polyolefin elastomers (a trademark of The Dow Chemical Company) and ENGAGE ^® (trademark of DuPont Dow Elastomers LLC), which can be prepared as described in U.S. Nos. 5,272,236 and 5,278,272; and radically high pressure polymerized ethylene polymers and copolymers such as low density polyethylene (LDPE), ethylene-acrylic acid copolymers (EAA copolymers) such as PRIMACOR ^™ (trademark of The Dow Chemical Company) and ethylene-vinyl acetate copolymers (EVA copolymers ) such as the poly mens Escorene ^™ (trademark of Exxon Chemical Company) and Elvax ^™ (trademark of EI du Pont de Nemours & Co.). The more preferred polyolefins are the homogeneously branched linear and substantially linear ethylene copolymers having a density (measured according to ASTM D-792) of 0.85 to 0.99 g / cm ³ , a ratio of weight average molecular weight to number average molecular weight (Mw / Mn). from 1.5 to 3.0, a measured melt index (measured according to ASTM D-1238) (190 / 2.16) of 0.01 to 100 g / 10 minutes and a 110/12 of 6 to 20 (measured according to ASTM D). 1238 (190/10)).

In general polyethylene has a high density (HDPE) has a density of at least about 0.94 grams per cubic centimeter (g / cm ³⁾ (ASTM Test Method D-1505). HDPE is usually made by similar processes to linear low density polyethylene. Such methods are disclosed in U.S. Patents 2,825,721; 2,993,876; 3,250,825 and 4,204,050. The HDPE is preferably used in the practice of the present invention has a density of 0.94 to 0.99 g / cm ³ and a melt index of from 0.01 to 35 grams per 10 minutes, as determined according to ASTM Test Method D-1238 ,

The Polysaccharides useful in the practice of the present invention Invention can be used are the different strengths, Celluloses, hemicelluloses, xylans, gums, pectins and pullulans. Polysaccharides are known and used, for example, in the Encyclopedia of Polymer Science and Technology, 2nd edition, 1987. The preferred polysaccharides are starch and cellulose.

The modified polysaccharides in practical use of the present invention are the esters and ethers of polysaccharides, such as cellulose ethers and cellulose esters or starch ester and starch ethers. Modified polysaccharides are known and are used, for example in the Encyclopaedia of Polymer Science and Technology, 2nd edition, 1987, described.

Of the As used herein, "starch" refers to carbohydrates natural of plant origin, mainly of amylose and / or Amylopectin, and includes unmodified starches; Strengths that dehydrated but not dried; physically modified starches, such as for example, thermoplastic, gelatinized or cooked starches; Strengths with a modified acid value (pH), where acid was added to the acid value a strength to lower to a range of 3 to 6; gelatinized starches, not gelatinized starches, networked strengths and split strengths (Strengthen, not in particulate Form). The strengths can present as granules, particles or powder. You can take off extracted from different plants, for example from potatoes, Rice, tapioca, corn, peas and cereals such as rye, Oats and wheat.

celluloses are known and used for example in the Encyclopedia of Polymer Science and Technology, 2nd edition, 1987. celluloses are polymers with a high content of natural carbohydrates (polysaccharides), which consist of anhydroglucose units, which by an oxygen bond are linked to long, substantially linear molecular chains. cellulose can be hydrolyzed to glucose. The degree of polymerization is sufficient from 1000 for Wood pulp up to 3500 for Cotton fiber, giving a molecular weight of 160,000 to 560,000 results. Cellulose can be made from plant tissue (wood, grass and cotton) be extracted. The celluloses can be used in the form of fibers become.

The Naturally occurring fibers or particulate fillers used in the practical Application of the present invention can be used for example, wood flour, wood pulp, wood fibers, cotton, flax, Hemp or ramie fibers, rice or wheat straw, chitin, chitosan, cellulosic materials derived from agricultural products, Nutshell flour, corncob flour and mixtures thereof.

in the Generally can the fibers of the present invention by well-known methods be prepared by, for example, melt spinning, wet spinning or bicomponent spiders. The fibers of the present invention can to any desired Size or Extruded length become. You can also to any desired Form are extruded, for example, to a cylindrical, cross-shaped, trilobal or ribbon-like cross section.

• (1) Side-by-side
• (2) Sheath-core
• (3) Islands-in-the-sea und
• (4) Citrus (Segmented-pie)

The bicomponent fibers of the present invention may have the following fiber cross-sectional structures:

• (1) Side-by-side
• (2) Sheath-core
• (3) islands-in-the-sea and
• (4) citrus (segmented pie)

(1) Side-by-side

One Process for the preparation of side-by-side bicomponent fibers is in U.S. Patent 5,093,061. In the process will be (1) two polymer streams separated by two openings passed and merged at substantially the same speed to side by side as a combined stream under the top of the spinneret with each other to merge; or (2) two polymer streams are separated, with im Essentially the same speed passed through openings on the Top of the spinneret to converge and side by side as a combined stream on the Top of the spinneret to merge together. In both cases, the speed is of each polymer stream at the point of fusion by velocity the metering pump and the size of the opening determined. The fiber cross section has a straight interface between two components.

Side-by-side fibers are generally used for making self-crimping Fibers used. All commercial selbstkräuselnden Fibers are made with the help of a system that works on the different Shrink values of each component based.

(2) Sheath-core

Sheath-core bicomponent are those fibers in which one of the components (core) completely from a second component (sheath) is surrounded. For the integrity of the fiber is the adhesion not always essential.

Sheath-core fibers become the most common prepared by a process in which two polymer liquids (Melting) separately to a location very close to the spinneret openings guided and then extruded in sheath-core form (sheath and core). With concentric fibers, the opening through which the "core" polymer is fed is in the middle of the spinneret outlet, and the flow conditions of the liquid Core polymer are precisely controlled to the concentric arrangement both components while spinning upkeep. Owing to Modifications of the spinneret openings You can get different forms of core and / or mantle inside of the fiber cross section.

The Sheath-core structure is used when the surface is the Property of one of the polymers, such as gloss, dyeability or resistance, while the core can contribute to strength and lower costs. The Sheath-core fibers are used in the nonwoven industry as crimp fibers and used as binding fibers.

The Sheath-core bicomponent fiber can be a core of the hydroxy-functionalized Polyether or polyester and a jacket of a polymer, the is not a hydroxy-functionalized polyether or polyester. Alternatively, the hydroxy-functionalized polyether or polyester the coat, and the polymer, which is not a hydroxy-functionalized Polyether or polyester is then the core of the bicomponent fiber. The sheath core may be circular in cross-section or may be a have different geometry and be trilobal, for example. It can for Example, a variant such as "tipped trilobal" are produced in which the sheath component around the core is no longer consistent, but only to the Tips of the lobes formed by the core is present. Other configurations, which can be used in the International Fiber Journal, Vol. 13, No. 3, June 1998, in the articles beginning on pages 20, 26 and 49 are described.

method for the production of sheath-core bicomponent fibers are in the U.S. Patents 3,315,021 and 3,316,336.

(3) Islands-in-the-sea

Islands-in-the-sea fibers are also referred to as matrix filament fibers, which are heterogeneous Include bicomponent fibers. A method of manufacture Iceland-in-the-sea fibers are described in U.S. Patent 4,445,833. The process becomes streams of core polymer through small tubes in jacket polymer streams being injected, being for each core stream a tube is available.

The combined sheath-core currents converge in the spinneret orifice and form a common islands-in-the-sea stream.

When the various polymer streams ge in the spinning process with a static mixer are also obtained islands-in-the-sea bicomponent fibers. In the static mixer, the polymer stream is divided again and again to form a matrix stream having a plurality of cores. This method of making islands-in-the-sea fibers is described in U.S. Patent 4,414,276.

Of the hydroxy-functionalized polyether or polyester can be the sea-polymer and the polymer which is not a hydroxy-functionalized polyether or polyester, may be the Iceland polymer. The hydroxy-functionalized Polyether or polyester may also be the Icelandic polymer, and the polymer that is not a hydroxy-functionalized polyether or polyester is, can be the sea-polymer.

The Islands-in-the-sea structure is used when desirable is to increase the fiber modulus, to reduce the moisture absorption, to reduce the dyeability, the Texturing to improve or the fiber a unique shiny To give appearance.

(4) citrus type (segmented pie)

The Citrus type or segmented pie type bicomponent fibers can be made be by polymer distribution and / or spinneret modifications of the The above-described methods used packing assemblies for manufacturing the side-by-side, sheath-core or islands-in-the-sea fibers. By doing for example, a first polymer stream and a second polymer stream alternately through eight radial channels instead of two channels Spinndüsenöffnung be supplied receives fiber is an eight-fiber citrus-type fiber. If the spinneret opening the Configuration of three or four slots on a circle has (a common opening configuration for the production of hollow fibers), the fiber is a hollow fiber from Citrus type with eight segments. The hollow fiber of the citrus type can also using special spinneret orifice configurations with a sheath-core spinpack, as in the US patents 4,246,219 and 4,357,290.

The Fibers of the present invention may be combined with other art or Natural fibers are mixed, for example with carbon fibers, cotton, Wool, polyester, polyolefin, nylon, rayon, glass fibers, fibers Silica, silica-alumina, potassium titanate, silicon carbide, Silicon nitride, boron nitride, boron, acrylic fibers, tetrafluoroethylene fibers, Polyamide fibers, vinyl fibers, protein fibers, ceramic fibers, such as For example, aluminum silicate, and oxide fibers such as boron oxide.

additives such as pigments, stabilizers, tougheners, plasticisers, carbon black, conductive metal particles, Abrasives and lubricating polymers can be added to the fibers become. The method of adding the additives is not critical. The additives can the hydroxy-functionalized polyether or polyester expediently be added before production of the fibers. When the hydroxy-functionalized Polyether or polyester is made in solid form, the Add additives to the melt prior to preparation of the fibers.

The Fibers of the present invention may be obtained by chemical treatment, warming or irradiation with UV light are crosslinked. For example, the Fibers with crosslinking agents such as diisocyanates, glycidyl methacrylate, Bisepoxides and anhydrides are chemically treated.

The Fibers of the present invention are suitable for use in Filter media, as binding fibers for Glass or carbon fibers, as bonding fibers in nonwoven fabrics of thermoplastic Polymers that are not hydroxy-functionalized polyethers or polyesters or as binder fibers in nonwoven webs of cellulosic materials. These fibers are also useful in the manufacture of medical clothing. They are also useful in the production of woven and nonwoven fabrics used in the manufacture of clothing, water-absorbing materials, antistatic wipes or water-absorbent mats can be used.

Textiles are prepared from the fibers of the present invention by methods manufactured, which are common in the weaving industry, for example by weaving or knitting.

• (1) Trockengeformt, kardiert oder airlaid und verfestigt – Die Vliese werden durch Kardieren oder Airlaying aus Stapelfasern gebildet, insgesamt oder in einem Muster mit Latex oder einem anderen wasserhaltigen Klebstoff verfestigt. Beim Kardieren werden Klumpen von Stapelfasern mechanisch zu einzelnen Fasern getrennt und zu einem zusammenhängenden Vlies geformt. Beim Airlaying werden Fasern in einen Luftstrom eingeleitet und auf einem Sieb aus dem Luftstrom abgefangen.
• (2) Thermoverfestigt – Trockengeformte Vliese aus Stapelfasern werden mit schmelzbaren Fasern verfestigt oder ganz aus schmelzbaren Fasern hergestellt.
• (3) Airlaid – Zellstofffasern, mit oder ohne zusätzliche Stapelfasern, werden mit Latex oder ähnlichen Klebstoffen verklebt.
• (4) Nassgeformt – Kurze Fasern werden nach Verfahren, die aus der Papierherstellung abgeleitet wurden, zu einem Vlies geformt und anschließend mit Latex oder thermischen Bindemitteln verklebt.
• (5) Spunbonded – Vliese aus langen Filamenten mit normalem Textildurchmesser werden direkt aus Blockpolymer hergestellt und normalerweise thermisch verfestigt.
• (6) Meltblown – Vliese aus langen Fasern mit extrem feinem Durchmesser werden direkt aus Blockpolymer hergestellt und normalerweise durch Heißprägeverfahren verfestigt.
• (7) Spunlaced – Trockengeformte Vliese werden mechanisch durch eine Vielzahl von feinen, unter hohem Druck stehenden Wasserstrahlen miteinander verschlungen, in den meisten Fällen ohne Klebstoff als Bindemittel.
• (8) Genadelt – Die Fasern werden durch eine Vielzahl von hin- und hergehenden Reihen von Hakennadeln mechanisch miteinander verschlungen.
• (9) Kaschiert – Verschiedene Schichten werden durch einen Klebstoff, durch Heißverschmelzen oder durch Verschlingen zu einem Verbundgewebe oder einem verstärkten Gewebe kombiniert.
• (10) Nähgewirkt – Stapelfaservliese werden mit Garnen, die in die Vliese eingenäht oder eingestrickt werden, verstärkt oder mechanisch umhüllt.

Nonwovens are based on a fiber fleece. From the fibers of the present invention, nonwovens can be made using the following known technologies:

• (1) Dry-formed, carded or airlaid and consolidated - The webs are formed by carding or airlaying from staple fibers, solidified in whole or in a pattern with latex or other hydrous adhesive. In carding, lumps of staple fibers are mechanically separated into individual fibers and formed into a coherent web. Airlaying turns fibers into air introduced stream and intercepted on a sieve from the air stream.
• (2) Thermo-consolidated - Dry-formed staple fiber nonwoven fabrics are solidified with fusible fibers or made entirely of fusible fibers.
• (3) Airlaid pulp fibers, with or without additional staple fibers, are bonded with latex or similar adhesives.
• (4) Wet-formed - Short fibers are formed into a nonwoven fabric by methods derived from papermaking and then bonded with latex or thermal binders.
• (5) Spunbonded nonwovens made of long filaments of normal textile diameter are made directly from block polymer and normally thermally solidified.
• (6) Meltblown nonwovens made of long fibers of extremely fine diameter are produced directly from block polymer and usually solidified by hot stamping.
• (7) Spunlaced - Dry-formed nonwovens are mechanically entangled with each other by a variety of fine, high-pressure jets of water, in most cases without adhesive as a binder.
• (8) Needled Needle - The fibers are mechanically entangled by a plurality of reciprocating rows of hook needles.
• (9) Laminated - Various layers are combined by adhesive, by heat fusion or by entanglement to form a composite fabric or a reinforced fabric.
• (10) Sewing - staple fiber webs are reinforced or mechanically wrapped with yarns sewn or knitted into the webs.

nonwovens and methods for their preparation are described in the Encyclopedia of Polymer Science And Engineering, 2nd Edition, Volume 10, pages 204-251, bechrieben.

The The following working examples serve to illustrate the invention and should not be construed as limiting its scope. If unless otherwise stated, all parts and percentages are by volume or volume percent.

example 1

One 3/8 inch (0.95 cm) single screw extruder with an 8-hole spinneret used to monofilaments based on 100 percent thermoplastic hydroxy-functional polyether to spin. The melting temperature was 200 ° C. The fibers were wound on spools without further stretching.

Example 2

It bicomponent fibers were spun, the polypropylene core and a thermoplastic hydroxy-functionalized polyether contained as a cloak. Two single screw extruders were used, from to which one supplied the polypropylene and the other, the thermoplastic hydroxy-functionalized polyether. The extruders led the molten polymers (the melting temperature was 200 ° C) of a 288-hole spinneret the bicomponent fibers were spun. There were fibers with a relationship from polypropylene to thermoplastic hydroxy-functionalized Polyether spun from 90:10, 80:20, 70:30, 40:60 and 50:50. The Fibers were added as well after exiting the spinneret stretched with the help of draw rolls and then on spools wound.

Example 3

A polyetheramine poly (hydroxy amino ether) (derived from the reaction of the diglycidyl ether of bisphenol A with ethanolamine) and a polypropylene were spun into bicomponent fibers. The poly (hydroxy amino ether) had an MFI (melt flow index) of 8 at 230 ° C under a 2.16 kg weight. The polypropylene source used was a Pro-fax ^™ PF635 polypropylene from Montell having an MFI of 35. This sheath-core bicomponent fiber was made under the conditions listed in Table I.

Table 1

Example 4

A Bicomponent fiber with a sheath of poly (hydroxyaminoether) (obtained from the reaction of the diglycidyl ether of bisphenol A with ethanolamine) and a polypropylene core with a weight ratio of 30/70 (w / w) was treated on a Tech Tex texturing line around her a ripple to rent. This system works according to the stuffer box texturing process. The textured yarn was printed on an Ace Strip Cutter, Model C-75, to staple fibers of a length cut from 2 inches (5 cm). After curling and pile cutting was the fiber on a 12 inch (30.5 cm) wide microdenier metal card in batches each opened by 30 grams. Out of the open Fiber was then made on a pattern card strand of a fiber fabric. This carded fiber lay on a James Hunter Fiberlocker Needle machine needled to a resulting needle felt.

Example 5

cotton fibers (4 kg, with a length from 1.5 to 5 cm) and bicomponent fibers of 7 denier (poly (hydroxy amino ether) / polypropylene in relation to 30/70 (w / w) (0.45 kg, with a length of 2.5 cm) were from Hand mixed and then opened. The mixture was carded and converted into a nonwoven fabric which was coated with Calender rolls at 170 ° C thermally solidified.

Example 6

Cotton linters (150 g) and bicomponent fibers of 7 denier (polyetheramine / polypropylene in the ratio 30/70 (w / w)) were placed in a cylindrical tank containing 300 L of water and the contents of the tank were stirred for 5 minutes. The polyetheramine was recovered from the reaction of the diglycidyl ether of bisphenol A with ethanolamine. The ratio of bicomponent fibers to cotton linters was 5 percent on a weight basis. The slurry was then pumped to a polyester mesh conveyor belt and the produced webs were removed. The wet webs were dried by passing them through a 165 ° C oven with a residence time of about 1 minute. The dried webs were then consolidated with heated calender rolls at temperatures of 100 ° C to 180 ° C. The basis weight of the nonwovens after solidification was about 90 g / m ² .

Example 7

A spunbond web of sheath-core bicomponent fibers was made under the conditions listed in Table II. The polyetheramine shell (recovered from the reaction of the diglycidyl ether of bisphenol A with ethanolamine) had an MFI of 15. The propylene core consisted of Pro-fax ^™ PF635 with an MFI of 35. The sheath / core ratio was 20/80 (w / w). The unit was operated at slot air pressures of 20, 25 and 30 psi and the spunbond material was removed from a vacuum-operated perforated conveyor belt. Withdrawal rates ranged from 50 to 75 meters per minute. The calender rolls were set at 60 ° C and appeared to provide sufficient solidification for dry nonwoven material.

Table II

Examples 8 to 15 - PHAE blends for hydrophilic Fiber / fabric applications

The poly (hydroxy amino ether) ("PHAE") used in the following Examples 8 to 15 was made by The Dow Chemical Company due to the polymerization of a diglycidyl ether of bisphenol A and ethanolamine. The PHAE had the following properties: number average molecular weight (Mn) = 14,000; weight average molecular weight (Mw) = 35,000; Melt index = 15 (measured at 190 ° C with a weight of 2.16 kg); Glass transition temperature (Tg) = 78 ° C. In these Examples 8 to 15, PEG denotes poly (ethylene glycol) and PEO denotes poly (ethylene oxide). PEG and PEO have the same polyoxyethylene repeat unit shown below: (-CH ₂ CH ₂ O-) _n

The designation of polymers having the above structure as PEG or PEO is based on the product name mentioned in an Aldrich catalog, ie PEG is used when the number average molecular weight (Mn) of polyoxyethylene is 10,000 or less; and PEO is used when the viscosity-average molecular weight (Mv) is 100,000 or more. In the following examples, the number immediately after PEG or PEO gives the calculated average molecular weight (Mn or Mv) from the Ald rich catalog.

EPE denotes a block copolymer having the general structure shown below: H (-OCH ₂ CH ₂ -) _x [-OCH (CH ₃ ) CH ₂ -] _y (-OCH ₂ CH ₂ -) _z OH

The EPE block copolymers contain a hydrophobic poly (propylene oxide) block having a molecular weight in the range of a minimum of 900 to a maximum of 4000 with two polyoxyethylene block hydrophilic blocks such that the total weight of the polyoxyethylene blocks is 10 to 90% by weight. of the entire molecule. The EPE block copolymers are nonionic surfactants [see LG Lundsted and IR Schmolka, "The Synthesis and Properties of Block Copolymer Polyol Surfactants" in Block and Graft Copolymerization, Vol. 2 (edited by RJ Ceresa), John Wiley and Sons, New York, Chapter 1, pp. 1-103]. The EPE block copolymers are marketed as polyols of PLURONIC ^® brand (BASF Wyandotte Corporation) and also from The Dow Chemical Co. sold (for example Polyglycol EP-1730 and EP 1660 ).

The here for nomenclature used in EPE block copolymers is called the weight percent ethylene glycol and the calculated average molecular weight (Mn) as in specified in the Aldrich catalog. For example, EPE-30 (Mn 5800) an EPE block copolymer containing 30 wt .-% ethylene glycol and a calculated number average molecular weight of 5800 has.

The following test methods were used for Examples 8 to 15:
The glass transition temperature (Tg) was determined using a differential scanning calorimeter DSC 2010 from TA Instruments. Samples (5 to 10 mg) were prepared in hermetically sealed dishes. Two test runs were performed for each sample. The first test run was from ambient to 200 ° C at 10 ° C per minute. The sample was then cooled to ambient or below with dry ice, after which the second test run was carried out at 10 ° C / minute to 200 ° C. The Tg value was determined from the inflection point of the second test run.

Of the pH7 buffer contact angle was for Molded films with a Krüss contact angle measuring system (goniometer) G40 with a fiber optic Eurometrix light source, a Kernco microscope G-1, a light source and a camera mount as well as with a camera of the type Krüss Panasonic CCTV and a Monitor WV-5410 was equipped. A small drop of pH7 buffer was added given the foil, and at the interface between foil, drops and air formed angle was calculated using the system software (G40 V1.32-US). In the following examples, the terms "water contact angle" and "pH7 buffer contact angle" are synonymous.

Laboratory fiber spinning of PHAE blends. The fiber spinning apparatus consisted of a Capillary melt rheometer of the brand Rheometrix, equipped with a 1000μm nozzle, a Rheotens attachment and a variable-speed roller with a Scope of 12 inches (30.5 cm) was equipped on which the fiber was spun.

Example 8 - PHAE blend with 10 wt% PEG 10,000

PHAE (243.0g) and PEG 10,000 (27.1g, Aldrich Chemical Co., Tm 63 ° C) 20 minutes in a big one Haake torque rheometer (with roller-type stirring blades) in an isothermal Metal temperature of 170 ° C and melt blended at a mixing speed of 100 rpm. The resulting mixture had a Tg of 53 ° C without crystalline Melting point. A compression molded film of the mixture was transparent and had a water contact angle of 67. Fiber was at 190 ° C with a Rheometer piston speed of 0.3 inches / minute and a take-up roll speed of 1780 rpm (543 m / min) melt spun. There were also others Mixtures with 5 and 25 wt .-% PEG 10,000 prepared, and the results are included in Table III.

Example 9 - PHAE mixture with 5% by weight of PEO 100,000

PHAE (57.1 g) and PEO 100,000 (3.1 g, Aldrich Chemical Co., Tm 65 ° C) were stirred in a Haake torque rheometer for 15 minutes at an isothermal metal temperature of 180 ° C and a mixing speed of 100 rpm melt-mixed. The resulting mixture had a Tg of 66 ° C with no crystalline melting point. A compression molded film of the blend was transparent and had a water contact angle of 68. Fiber was heated at 190 ° C at a piston speed of 0.3 inches / minute (8 mm / minute) and a take up speed of 1780 rpm (543 m / min ) melt-spun. The denier value of the fiber was 9 g (equal to the weight of 9000 m continuous fiber). In addition, more Mischun 10 percent and 25 percent PEO 100,000, respectively, and the results are included in Table III.

Example 10 - PHAE mixture with 5% by weight PEO 4,000,000

PHAE (57.0g) and PEO 4,000,000 (3.0g, Aldrich Chemical Co., Tm 65 ° C) in a Haake torque rheometer for 20 minutes at an isothermal Metal temperature of 180 ° C and melt blended at a mixing speed of 100 rpm. The resulting mixture had a Tg of 67 ° C without crystalline Melting point. A compression molded film of the mixture was transparent and had a water contact angle of 65. Fiber was at 190 ° C with a Piston speed of 0.3 inches / minute (8 mm / minute) and a Winding speed of 1780 rpm (543 m / min) melt-spun. Of the Denier value of the fiber was 10 g.

Example 11 - PHAE mixture with 10 wt% PEO 4,000,000

PHAE (243.0 g) and PEO 4,000,000 (27.0 g, Aldrich Chemical Co., Tm 65 ° C) in a Haake torque rheometer 25 minutes in an isothermal Metal temperature of 180 ° C and melt blended at a mixing speed of 100 rpm. The resulting mixture had a Tg of 55 ° C without crystalline Melting point. A compression molded film of the mixture was transparent and had a water contact angle of 72. Fiber was at 190 ° C with a Piston speed of 0.3 inches / minute (8 mm / minute) and a Winding speed of 1780 rpm (543 m / min) melt-spun.

Example 12 - PNAE Blend with 15% by weight of PEO 4,000,000

PHAE (51.0 g) and PEO 4,000,000 (9.0 g, Aldrich Chemical Co., Tm 65 ° C) in a Haake torque rheometer for 20 minutes at an isothermal Metal temperature of 180 ° C and melt blended at a mixing speed of 100 rpm. The resulting mixture had a Tg of 44 ° C without crystalline Melting point. A compression molded film of the mixture was transparent and had a water contact angle of 42. Fiber was at 190 ° C with a Piston speed of 0.3 inches / minute (8 mm / minute) and a Winding speed of 1100 rpm (335 m / min) melt-spun. It Further blends were made with 20 and 25% PEO 4,000,000, and the results are included in Table III.

Example 13 - PHAE mixture with 3.7% by weight EPE-30 (Mn 5800)

PHAE (73.4g) and EPE-30 (2.8g, Aldrich Chemical Co., Tm 39 ° C) in a Haake torque rheometer for 20 minutes at an isothermal Metal temperature of 180 ° C and melt blended at a mixing speed of 100 rpm. The resulting mixture had a Tg of 69 ° C without crystalline melting point. A compression molded film of the mixture had a pearlescent shiny, semi-transparent appearance and had a water contact angle of 24th fiber was at 200 ° C at a piston speed of 0.3 inches / minute and a take-up speed of 1780 rpm (543 m / min) melt spun. The denier value of produced fiber was 8 g. A small hand pattern of the nonwoven fabric was made from the fiber as follows: Part of the fiber (1.4 g) was cut into 2 inch long staple fibers and made into a Fleece cards. The fleece was folded and then through a Beloit Wheeler Model 700 laboratory calender roll. The Calender rolls were at 210 ° F and 1000 psi, which is a well-consolidated nonwoven fabric revealed. With a similar one Procedure was a nonwoven fabric from a sample of a pure PHAE fiber (1.4 g). The ability of nonwovens, water was sucked up, then checked by placing one end of a small strip (19 x 81 mm) of each nonwoven fabric was dipped in deionized water and the time was measured who needed the water to get on the fabric strip up to one in at a distance of 25 mm from the surface of the water. The PHAE blend with EPE-30 (Mn 5800) sucked the water in 2.5 Minutes up to the line while the non-woven fabric made of pure PHAE water did not absorb at all. The Nonwovens were again dried and the absorbent test became repeated three times. Each time the same results were found - the with The nonwoven fabric made from the EPE-30 blend absorbed water and the non-woven fabric of pure PHAE not.

Example 14 - PHAE blend with 5 wt.% EPE-80 (Mn 8400)

PHAE (57.0 g) and EPE-80 (3.0 g, Aldrich Chemical Co., Tm 58 ° C) were stirred in a Haake torque rheometer for 20 minutes at an isothermal metal temperature of 180 ° C and a mixing speed of 100 U / min melt blended. The resulting mixture had a Tg of 64 ° C with no crystalline melting point. A compression molded film of the mixture was transparent and in contact with water The fiber was melt spun at 200 ° C at a piston speed of 0.3 inches / minute and a take up speed of 850 rpm (259 m / min). The denier value of the produced fiber was 274 g.

mixtures PHAE with other EPE block copolymers, including EPE-30 (Mn 4400); EPE-40 (Mn 2900); and EPE-50 (Mn 1900) were also still analogous to methods made to those described above. The results for this Mixtures are listed in Table IV.

Example 15 - PNAE blend with 5% by weight of poly (propylene glycol) (Aldrich, Mn 3500

• a) Gewichtsprozent des zugegebenen Zusatzstoffes, der Rest ist PHAE.
• b) Kontaktwinkelmessung für Tropfen von pH7-Pufferlösung auf der Oberfläche einer formgepressten Folie. Der angegebene Wert ist der Durchschnitt der Ergebnisse für 15 Tropfen.
• c) Proben wurden als mischbar eingestuft, wenn der Tg-Wert die Fox-Gleichung erfüllt hat und wenn Filme aus den Mischungen transparent waren.

Tabelle IV PNAE-Mischungen mit EPE-Blockcopolymeren

• a) Gewichtsprozent des zugegebenen Zusatzstoffes, der Rest ist PHAE.
• b) Kontaktwinkelmessung für Tropfen von pH7-Pufferlösung auf der Oberfläche einer formgepressten Folie. Der angegebene Wert ist der Durchschnitt der Ergebnisse für 15 Tropfen.
• c) Proben wurden als mischbar eingestuft, wenn der Tg-Wert die Fox-Gleichung erfüllt hat und wenn Filme aus den Mischungen transparent waren.

PHAE (64.9 g) and poly (propylene glycol) (3.4 g) were melt blended in a Haake torque rheometer for 40 minutes at an isothermal metal temperature of 150 ° C to 180 ° C and a mixing speed of 30 to 100 rpm. The initial mix seemed to be biphasic and the blending was very poor. Temperature and mixing speed were adjusted until good mixing was achieved. The resulting mixture had a Tg of 76 ° C. A compression molded film of the mixture was opaque. Table III PHAE blends with polyoxyethylene (PEG or PEO)

• a) weight percent of the added additive, the remainder being PHAE.
• b) Contact angle measurement for drops of pH7 buffer solution on the surface of a compression molded film. The given value is the average of the results for 15 drops.
• c) Samples were considered miscible if the Tg value met the Fox equation and if films from the mixtures were transparent.

Table IV PNAE blends with EPE block copolymers

• a) weight percent of the added additive, the remainder being PHAE.
• b) Contact angle measurement for drops of pH7 buffer solution on the surface of a compression molded film. The given value is the average of the results for 15 drops.
• c) Samples were considered miscible if the Tg value met the Fox equation and if films from the mixtures were transparent.

Claims (23)

A fiber of at least one thermoplastic hydroxy-functionalized polyether selected from: (1) polyetheramines having repeating units represented by the formula:

(2) hydroxy-functionalized polyethers having repeating units represented by the formula:

or (3) hydroxy-functionalized poly (ether sulfonamides) having repeating units represented by the formula:

or

wherein R ^{5 is} hydrogen or alkyl; R ⁷ and R ^{8 are} independently alkyl, substituted alkyl, aryl, substituted aryl; R ^{9 is} a divalent organic component which is mainly hydrocarbon; A is an amine moiety or a combination of different amine moieties; B is a divalent organic component which is mainly hydrocarbon; and m is an integer of 5 to 1000. The fiber of claim 1, wherein the thermoplastic hydroxy-functionalized polyether is prepared by reacting a dinucleophilic monomer with a diglycidyl ether, a diglycidyl ester or epihalohydrin. A fiber according to claim 1, which has a cylindrical, cross-shaped, trilobal or ribbon-like Cross section has. Fiber according to claim 1, obtained by melt spinning, Dry spinning or wet spinning of a polymer solution is formed. Fiber according to claim 1 in the form of a filter medium, a binding fiber for Glass or carbon fibers, a binder fiber in nonwovens a thermoplastic polymer that is not hydroxy functionalized Polyether, or a binder fiber in nonwoven materials cellulose-based or in the form of a medical garment. Woven or nonwoven fabric that claims the fiber 1 and, optionally, a synthetic or natural fiber. A fabric according to claim 6, wherein the synthetic fiber is a polyester, a polyamide, rayon or a polyolefin and the Natural fiber is cotton. Fabric according to claim 6 in the form of a garment, a water-absorbent cloth, a filter cloth, a battery separator, an antistatic cloth or a water-absorbent mat. The fiber of claim 1 from a mixture of or more hydroxy-functionalized polyethers with a thermoplastic Polymer which is not a hydroxy-functionalized polyether and is selected of a polyolefin, polyester, polyamide, polysaccharide, modified Polysaccharide or natural occurring fiber or particulate Filler, thermoplastic polyurethane, thermoplastic elastomer or glycol-modified copolyester (PETG). A fiber according to claim 1 which is a bicomponent fiber is with (1) a first component of a thermoplastic hydroxy-functionalized polyether or a mixture of a hydroxy-functionalized polyether and (2) a second component of a polyolefin, polyester, polyamide, polysaccharide, modified Polysaccharide or natural occurring fiber or particulate Filler, thermoplastic polyurethane, thermoplastic elastomer or glycol-modified copolyester (PETG). A bicomponent fiber according to claim 10, wherein the hydroxy-functionalized polyether is prepared by reacting a dinucleophilic monomer with a diglycidyl ether, a diglycidyl ester or epihalohydrin. A bicomponent fiber according to claim 10 or 11, wherein it is a side-by-side bicomponent fiber, a sheath-core bicomponent fiber, a segmented pie bicomponent fiber or an islands-in-the-sea bicomponent fiber is. A bicomponent fiber according to claim 12, having a core from the thermoplastic hydroxy-functionalized polyether and a jacket of a thermoplastic polymer that is not hydroxy functionalized Polyether is. A bicomponent fiber according to claim 13, having a sheath from the thermoplastic hydroxy-functionalized polyether and a core of a thermoplastic polymer that is not hydroxy functionalized Polyether or polyester is. A bicomponent fiber according to claim 11, which has a cylindrical, cross-shaped, trilobal or ligamentous Cross section has. A bicomponent fiber according to claim 11 in the form of a Filter medium, a binding fiber for glass or carbon fibers, a binder fiber in nonwoven fabrics of a thermoplastic polymer, which is not a hydroxy-functionalized polyether or polyester, or a binder fiber in nonwovens of cellulosic materials or in the form of a medical garment. Woven or nonwoven fabric that claims the fiber 11 and, optionally, comprises a synthetic or natural fiber. The fabric of claim 17, wherein the synthetic fiber is a polyester, a polyamide, rayon or a polyolefin and the Natural fiber is cotton. The fabric of claim 17 in the form of a garment, a water-absorbent cloth, a filter cloth, a battery separator, an antistatic cloth or a water-absorbent mat. A fiber according to claim 1 comprising a mixture of: (a) a poly (hydroxy amino ether) having repeating units represented by the formula:

wherein A is a diamine moiety or a combination of different amine moieties; B is a divalent organic moiety which is predominantly hydrocarbylene; R is alkyl or hydrogen; and n is an integer of 5 to 1000; and (b) at least one of a polyethylene glycol, poly (ethylene oxide) or EPE block copolymer. A fiber according to claim 20, wherein the poly (hydroxy amino ether) the reaction product of a diglycidyl ether of bisphenol A and Ethanolamine is. A method for producing a nonwoven fabric by Forming a web of at least one fiber component and heating the web Fleece, so that the fiber components of the nonwoven stick, thereby characterized in that at least one fiber component of a thermoplastic hydroxy-functionalized polyether according to claim 1. The method of claim 22 wherein at least one fiber component consists of a poly (hydroxy amino ether) having repeat units represented by the formula:

wherein A is a diamine moiety or a combination of different amine moieties; B is a divalent organic moiety which is predominantly hydrocarbylene; R is alkyl or hydrogen; and n is an integer greater than 10.